Organic bases were first used as effective catalysts for the synthesis of propylene carbonate from propylene glycol and carbon dioxide in the presence of acetonitrile. Acetonitrile in the reaction acted as not only the solvent but also the dehydrating reagent to remove the water produced from the reaction. It was interesting that upon ammonium carbonate being introduced into the reaction system, the catalytic selectivity was significantly enhanced. With 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the catalyst, the yield of propylene carbonate could reach 15.3% with the selectivity of 100% under the optimal conditions.